Silver halide photographic compositions containing a sulfinamide as a fog inhibitor



United States Patent 40/ 47,778 Int. Cl. G03c 1/34, 1/28 US. Cl. 96-109 13 Claims ABSTRACT OF THE DISCLOSURE A silver halide photographic composition in which the formation of fog is substantially inhibited by the addition of a sulfinamide compound having the general formula:

The present invention relates to a silver halide photographic material and more particularly to a silver halide photographic composition in which the formation of fog is substantially inhibited by the addition of a sulfinamide compound.

It is Well known that silver halide photographic material tends to become spontaneously developable on storage without any exposure to light. There are normally detectable amounts of silver salts reduced during development in the areas where no exposure has occurred; this is commonly called fog. The formation of fog is promoted in the case where the silver halide photographic emulsion is sensitized by ripening or reacting at an elevated temperature and/ or for a long period of time. Moreover, when chemical sensitizers, such as a sulfur compound, a noble metal compound, a polyalkylene oxide derivative, or a reducing compound is incorporated in the silver halide composition for increasing the sensitivity of the photographic emulsion, the formation of fog is particularly enhanced. Silver halide photographic compositions which are subjected to the above-mentioned sensitizing treatment are usually plagued with the for mation of fog even directly after manufacture and formation of fog is considerably increased on storage. Accordingly, in order to inhibit the formation of fog, an anti-foggant has been employed. The most effective antifoggant is selected in accordance with the kinds of silver halide photographic compositions, the system of manufacturing the photographic compositions, the method for sensitizing the silver halide photographic emulsion, and the kinds of chemical sensitizers. There have hitherto been proposed many compounds as antifoggants, among which many effective ones have been found.

In this invention it has been found that the formation of fog in silver halide photographic compositions can be markedly inhibited by incorporating in the silver halide photographic emulsion a sulfinamide compound during the production of silver halide photographic elements. The sulfinamide compounds shown by the general Formula I that have never been employed in silver halide photographic compositions. They are:

R2 t R Ha (I) wherein R represents a hydrogen atom, a halogen atom or a methyl group and R and R represents a hydrogen atom, a lower alkyl group, an aryl group, or an arlakyl group; said R may be combined with said R to form a heterocyclic group.

Typical examples of the sulfinamide compounds shown by the above-mentioned general Formula I are shown below but it should be understood that the compounds to be used in this invention are not limited to these specific o-nes only. Compound 1: (H)

orn-Q-s-mn mp. 117-118 C: Compound 2: (H) /C2H5 CH s N CzHs Compound 3: O CH2CH2 ll CH3- S N O CHzOHz mp. -121 0. Compound 4: g

m.p. 112-1l4 0.

Compound 5: 0 CH2CH2 ll SN\ /CH2 CHzCHz 111.1). 79-8l C. Compound 6: (I?

mp. 108-109" C. Compound 7: (1)] SNH Cl Compound 8:

These sulfinamide compounds may .be prepared by the reaction of a corresponding amine and the sulfinchloride prepared from a corresponding sulfinic acid.

The above-mentioned compounds of this invention may be added alone or as mixtures thereof. Further, the sulfinamide compound may be incorporated in the photographic emulsion in any stage of the production of silver halide photographic elements, but the best result is obtained by incorporating it before chemical ripening or reaction. i

There is no particular limitation about the addition amount of the compound and the optimum amount thereof is varied according to the kind of the compound to be employed, but in general, the suitable amount is 0.02400 g., preferably 02-20 g. per 1 mol of silver halide in the photographic emulsion.

The photographic emulsions that are used in this invention may be optically dye sensitized. Moreover the photographic emulsion may be chemically sensitized with sulfur compounds, noble metal salts, polyalkylene oxide derivatives, reducing compounds and the like. In particular, the antifogging effect by the compounds of this invention are remarkable when the photographic emulsion has been sensitized with a gold salt. Further, it may be noted that in cases where the photographic emulsion contains a hardening agent, a natural or synthetic surface active agent and other stabilizers or antifoggants than the antifoggant of this invention, the compound of this invention can inhibit effectively the formation of fog without giving adverse influences on the desired photographic properties of these additives.

The following examples will serve to illustrate the present invention but are not to be construed as limiting the invention.

EXAMPLE 1 In a gelatinous, silver iodo-bromide emulsion for use in negative type, highly sensitive photographic material by neutral process (silver iodide 5.0 mol percent and silver bromide 95.0 mol percent) there was incorporated a methanol solution of p-toluene sulfinamide (Compound 1) of N,N diethyl-p-toluene sulfinamide (Compound 2) when starting the second reaction (chemical ripening) in an amount shown in the table below. Thereafter, g. of a sensitizing gelatin which was considered to contain a natural sulfur sensitizer was added into the emulsion together with 1.0 mg. of the gold sensitizer HAuCl -4H O and 80 mg. of KSCN as the aqueous solutions thereof and then the second ripening of the emulsion was conducted for 60 min. at 50 C. with stirring. Then, after the addition of 30 mg. of l,l'- diethyl-2,2-cyanine iodide, 0.45 g. of chromium alum, and 0.12 of saponin, the silver halide emulsion was applied to a cellulose triacetate film base and dried.

The photographic film was wedge-exposed to 5400 K. for sec., and then developed for 10 minutes at 20 C., in the developer having the following composition:

N-Methyl-p-aminophenol sulfate g 2.0 Sodium sulfite (anhydrous) g 100.0 Hydroquinone g 5.0 Borax g 2.0 Water to make liter 1 The results of the measurement of fog in the thus developed photographic films ofthis invention are shown in the following table contrasted with the results of cases without incorporating into the silver halide emulsion ptoluene sulfinamide or diethyl-p-toluene sulfonamide, thus indicating that the formation of fog was clearly inhibited by the addition of the compound of this invention.

A silver chloro-brornide photographic emulsion (silver bromide 70 mol percent and silver chloride 30 mol percent) by neutral process for use in fine grain positive type photographic film was gelled, sliced, washed with water, and, after the addition of 120 mg. of sodium thiosulfate per 1 mol of silver halide in the emulsion, subjected to a second ripening for 30 minutes at 52 C. The thus treated emulsion was divided into two equal parts, one of which was mixedwith the methanol solution of 1.5 g. per 1 mol of silver halide of p-toluene sulfinyl morpholine (Compound 3) or 1.0 g. per 1 mol .of silver halide of N- phenylbenzene sulfinamide (Compound 4) while another part of which was mixed with the same amount of only methanol as a control sample. Then both emulsions were subjected to ripening for a further 30 minutes at 52 C. The photographic emulsions were applied to cellulose triacetate film bases and then dried to provide light-sensitive photographic films having emulsion layers of 12 microns in thickness.

Thereafter, the hotographic films were exp d to 2660 K. for second, developed for 4 minutes at 20 C., in a developer having the following composition:

and then, after water-rinsing and drying, a sensitometric reading was conducted with the thus processed photographic films. The results shown in the following table illustrate that by the addition of the compound of this invention, the formation .of fog was inhibited with hardly any reduction of the relative sensitivity.

Relative sensitivity Fog density None 100 0. 09 Compound 3- 99 O. 06 Compound 4. 99 0. 07

EXAMPLE 3 A gelatinous silved iodo-bromide emulsion by ammonia process for use in X-ray films (silver iodide 2.2 mol percent and silver bromide 97.8 mol percent) was, when starting the secondripening reaction, mixed with a methanol solution of benzene sulfinyl pyridine (Compound 5) or N-benzylbenzene sulfinamide (Compound 6) in an amount shown in the table below. Then with 1.2 ml. of a methanol solution containing 0.01% by weight of triethyl thiourea, and after the further addition of a mixed solution of 5.0 ml. of an aqueous solution of HAuCl -4H O and 4.0 ml. of a 0.1 N aqueous solution of NH SCN, the emulsion was subjected to a second ripening for 60 minutes at 50 C.

The emulsion was then mixed with 0.2 g. per mol of silver halide of chromium alum and 0.2 g. per mol of silver halide of saponin and applied to a cellulose triacetate film base followed by drying to provide a light-sensitive film having an emulsion layer of 12 microns in thickness.

The photographic film was exposed to 5400 K. for second and then developed for 4 minutes at 20 C. in the developer havingvthe following composition:

N-methyl-p-aminophenol sulfate g 4.0 Sodium sulfite (anhydrous) g 60.0 Hydroquinone g 10.0 Sodium carbonate (mono-hydrate) g 53.0 Potassium bromide g 3.0 Water to make liter 1 Relative sensitivity Fog density None 100 O. 26 Compound 5:

10 g./mol AgX 196 0. 17

15 g./mo1 AgX 94 0. 12 Compound 6:

10 g./mol AgX-. 98 0. 19

15 g./mol AgX 96 0. 14

EXAMPLE 4 A gelatinous silver iodo-bro-mide emulsion (silver iodide 5.0 mol percent and silver bromide mol percent) by neutral process for use in high-sensitive negative type photographic films subjected to sulfur sensitization and gold sensitization was, directly before coating, mixed with a methanol solution of N-p-chlorophenylbenzene sulfinamide (Compound 7) in an amount shown in the table below and coated on a glass plate followed by'drying to provide a photographic light-sensitive glass plate having the emulsion layer of 20 microns thickness.

After preserving the dry plate for 3 days at 50 C., and for 7 days at 50 C., and at a humidity of 80% RH, the dry plate was exposed to 5400 K., for V second and developed in the developer having the following composition for 10 minutes at 20 C.

N-methyl-p-aminophenol sulfate g 2.0 Sodium sulfite (anhydrous) g 100.0 Hydroquinone g 5.0 Borax g 2.0 Water to make liter 1 The relative sensitivity and the fog density of the thus developed dry plate were measured and the results compared with those of a dry plate having no compound of this invention as shown in the following table. This then indicates that the formation of fog caused by preservation was clearly inhibited by the addition of the antifoggant of this invention.

A gelatinous silver iodo-bro-mide emulsion (silver iodide 2.2 mol percent and silver bromide 97.8 mol percent) by the ammonia process for use in X-ray photographic film that had been subjected to a sulfur sensitization and a gold sensitization was, directly before coating, mixed with a methanol solution of p-chlorobenzene sulfinyl morpholine (Compound 8) in an amount shown in the table below, and then coated on a glass plate followed by drying to provide a dry plate having thereon the light-sensitive emulsion layer of 19 microns in thickness.

After preserving the dry plate for 3 days at 50 C., and then for 5 days at 50 C., and at 80% RH, the dry plate was exposed to 5400 K. for second and developed for 4 minutes at 20 0., in the developer having the following composition:

N-methyl-p-aminophenol sulfate g 4.0 Sodium sulfite (anhydrous) g 60.0 Hydroquinone g 10.0 Sodium carbonate (mono-hydrate) g 53.0 Potassium bromide g 3.0

Water to make liter 1 Thus processed dry plate was then measured for relative sensitivity and fog density, and the results thereof shown in the following table together with those of a control sample which had been prepared by the same conditions as above except that the compound of this invention had not been incorporated in the silver halide emulsion, showing that the formation of fog caused by storage was clearly inhibited.

(A): Relative density; (B): Fog density.

What we claim is:

1. A silver halide photographic light-sensitive composi tion comprising a support and a light-sensitive silver halide emulsion layer having incorporated therein at least one sulfinamide compound represented by the general formula:

wherein R represents a member selected from the group consisting of a hydrogen atom, a methyl group and a halogen atom; and R and R represent a member selected from the group consisting of a hydrogen atom, a lower alkyl group, an aryl group and an aralkyl group; said group R may be combined with said group R to form one heterocyclic group.

2. The silver halide photographic light-sensitive composition as claimed in claim 1 wherein the amount of said sulfinamide compound in the emulsion is 0.02400 g., based on 1 mol of the silver halide in the emulsion.

3. The silver halide photographic light-sensitive composition as claimed in claim 1 wherein the amount of said sulfinamide compound in the emulsion is 0L2-20 g., based on 1 mol of the silver halide in the emulsion.

4. The silver halide photographic light-sensitive composition as claimed in claim 1 wherein the silver halide light-sensitive emulsion has been ripened during or after incorporation of the sulfinamide compound.

5. The silver halide photographic light-sensitive composition as claimed in claim 1 wherein said silver halide emulsion is presensitized.

6. The silver halide photographic light-sensitive composition as claimed in claim 1 wherein said compound is p-toluene sulfinamide.

7. The silver halide photographic light-sensitive composition as claimed in claim 1 wherein said compound is N-diethyl-p-toluene sulfinamide.

8. The silver halide photographic light-sensitive composition as claimed in claim 1 wherein said compound is p-toluene sulfinyl morpholine.

9. The silver halide photographic light-sensitive composition as claimed in claim 1 wherein said compound is N-phenylbenzene sulfinamide.

10. The silver halide photographic light-sensitive composition as claimed in claim 1 wherein said compound is benzenesulfinyl pyperidine.

11. The silver halide photographic light-sensitive composition as claimed in claim 1 wherein said compound as N-benzylbenzene sulfinyl pyperidine.

12. The silver halide photographic light-sensitive composition as claimed in claim 1 wherein said compound is N-p-chlorophenylbenzene sulfonamide.

13. The silver halide photographic light-sensitive composition as claimed in claim 1 wherein said compound is p-chlorobenzene sulfinyl morpholine.

References Cited Chemical Abstracts, Vol. 17, p. 1445. Chemical Abstracts, Vol. 30, p. 89.

NORMAN G. TORCHIN, Primary Examiner R. LYONS, Assistant Examiner U.S. Cl. X.R. 96-107 

